Unraveling local structures of Salt-in-Water and Water-in-Salt electrolytes via ab initio molecular dynamics

Malaspina, Thaciana; Colherinhas, Guilherme; Weitzner, Stephen E.; Wood, Brandon C.; Eterno Fileti, Eudes

doi:10.1016/j.molliq.2023.122097

Title: Unraveling local structures of Salt-in-Water and Water-in-Salt electrolytes via ab initio molecular dynamics

Journal Article · 13 May 2023 · Journal of Molecular Liquids

DOI: https://doi.org/10.1016/j.molliq.2023.122097 · OSTI ID:2212863

Malaspina, Thaciana ^[1];

^[2];

^[3]; Wood, Brandon C. ^[3]; Eterno Fileti, Eudes ^[1]

Federal University of São Paulo, São José dos Campos, São Paulo (Brazil)
Federal University of Goiás, Goiânia, GO (Brazil)
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Water-in-salt electrolytes (WiSE) are attractive for electrochemical energy storage applications owing to their wide electrochemical stability windows and inherent safety. The high concentration of salts is widely known to suppress the decomposition of water, which otherwise limits the stability of conventional aqueous salt-in-water electrolytes (SiWE). Nevertheless, the microstructural features of WiSE that lead to this enhanced stability have not yet been fully elucidated. In this work, ab initio molecular dynamics simulations were performed to study the energetic, structural, and spectroscopic properties of LiTFSI SiWE and WiSE solutions. A detailed mapping of water-water and water-anion hydrogen bonding and cation–anion electrostatic interactions is reported for both electrolytes. Structural features are presented in terms of both radial and spatial distribution functions. Analysis of IR and vibrational power spectra reveal key differences in the intermolecular interactions in SiWE and WiSE that arise from modified solvation shell structures. Finally, the results obtained herein reveal the most important structural and spectroscopic differences between the electrolytes in normal and superconcentrated concentrations.

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Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); National Council for Scientific and Technological Development (CNPq); Fundação de Amparo à Pesquisa do Estado de Goiás (FAPEG); Improvement Coordination of Higher Education Personnel (CAPES); Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Grant/Contract Number:: AC52-07NA27344; GC 304903/2020-5; EEF 408290/2021-8; PRONEX-201710267000503; PRONEM-201710267000540; EEF 2020/16467-9

OSTI ID:: 2212863

Alternate ID(s):: OSTI ID: 1999676

Report Number(s):: LLNL-JRNL-857209; 1086755; TRN: US2406975

Journal Information:: Journal of Molecular Liquids, Vol. 383, Issue no. 1; ISSN 0167-7322

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Unraveling local structures of Salt-in-Water and Water-in-Salt electrolytes via ab initio molecular dynamics

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